1. Field of the Invention
The invention relates to a dispersion powder composition which is redispersible in water and is based on water-insoluble polymers, process for its preparation and its use.
2. Background Art
Dispersion powder compositions which are redispersible in water and are based on homo- or copolymers are known. Such a dispersion powder composition is prepared by spray drying the corresponding aqueous plastics dispersions in a stream of hot-air. The dispersion powders are suitable as additives to hydraulic binders in the building materials industry, and such products are furthermore employed as binders in coating compositions or in adhesives.
EP-A 228657 (U.S. Pat. No. 4,704,416) describes dispersion powders which are redispersible in water and are based on water-soluble polymers, and which comprise organic silicon compounds, preferably organopolysiloxanes. The dispersion powders are prepared by spray drying an emulsion of the organic silicon compound in an aqueous solution of the water-soluble polymer.
EP-B 279373 relates to powders which are redispersible in water and comprise organopolysiloxane, and which additionally comprise a water-soluble, film-forming polymer. They are prepared by spray drying the aqueous mixtures of the constituents mentioned.
EP-A 493168 relates to dispersion powders which are redispersible in water and are based on film-forming, water-insoluble vinyl or acrylic polymers, and which comprise silicones, more precisely organosiliconates and/or organopolysiloxanes. They are prepared by spray drying aqueous dispersions of the vinyl or acrylic polymers, to which silicones have been added before the spraying.
The invention is based on the object of providing dispersion powder compositions which are redispersible in water and are based on water-insoluble polymers, and which are modified with organosilicon compounds.
The invention relates to a dispersion powder composition which is redispersible in water and is based on water-insoluble organopolymers, wherein the powder composition comprises 0.1 to 30% by weight, based on the organopolymer content, of one or more water-dispersible silicon compounds having a boiling point under normal pressure of  greater than 160xc2x0 C., from the group consisting of silanes, polysilanes, oligosiloxanes, carbosilanes, polycarbosilanes, carbosiloxanes, polycarbosiloxanes and polysilylenedisiloxanes.
Suitable water-insoluble organopolymers are: homo- and copolymers which are in the form of an aqueous dispersion or which can be converted into an aqueous dispersion, and which, if appropriate at elevated temperature and/or in an alkaline medium, form a solid film after drying on and, if appropriate, hardening. The average particle size of the dispersion powder particles is in general 1 to 1000 xcexcm, preferably 10 to 700 xcexcm, particularly preferably 50 to 500 xcexcm.
Preferred water-insoluble polymers are:
vinyl ester homo- or copolymers containing one or more monomer units from the group consisting of vinyl esters of unbranched or branched alkylcarboxylic acids having 1 to 15 C atoms;
(meth)acrylic acid ester homo- or copolymers containing one or more monomer units from the group consisting of methacrylic acid esters and acrylic acid esters of unbranched or branched alcohols having 1 to 12 C atoms;
homo- or copolymers of fumaric and/or maleic acid mono- or diesters of unbranched or branched alcohols having 1 to 12 C atoms;
homo- or copolymers of dienes, such as butadiene or isoprene, and of olefins, such as ethene or propene, it being possible for the dienes to be copolymerized, for example, with styrene, (meth)acrylic acid esters or the esters of fumaric or maleic acid;
homo- or copolymers of vinyl aromatics, such as styrene, methylstyrene or vinyltoluene;
homo- or copolymers of vinyl-halogen compounds, such as vinyl chloride.
Where appropriate, water-insoluble, film-forming polyaddition and polycondensation polymers, such as polyurethanes, polyesters, polyethers (excluding polyethylene oxide), polyamides, melamine-formaldehyde resins or phenol-formaldehyde resins, if appropriate also in the form of their oligomeric precursors, are also suitable.
Preferred vinyl esters are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methylvinyl acetate, vinyl pivalate and vinyl esters of xcex1-branched monocarboxylic acids having up to 10 C atoms, for example VeoVa9R or VeoVa10R. Vinyl acetate is particularly preferred.
Preferred methacrylic acid esters or acrylic acid esters are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, t-butyl acrylate, n-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl acrylate. Methyl acrylate, methyl methacrylate, n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferred.
Preferred ester groups of fumaric and maleic acid are the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, t-butyl, hexyl, ethylhexyl and dodecyl group.
If appropriate, the vinyl ester copolymers can comprise 1.0 to 65% by weight, based on the total weight of the comonomer phase, of xcex1-olefins, such as ethylene or propylene, and/or vinyl aromatics, such as styrene, and/or vinyl halides, such as vinyl chloride, and/or acrylic acid esters or methacrylic acid esters of alcohols having 1 to 10 C atoms, such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, t-butyl acrylate, n-butyl methacrylate, t-butyl methacrylate and 2-ethylhexyl acrylate and/or ethylenically unsaturated dicarboxylic acid esters or derivatives thereof, such as diisopropyl fumarate, or the dimethyl, methyl t-butyl, di-n-butyl, di-t-butyl and diethyl ester of maleic acid or fumaric acid, or maleic anhydride.
If appropriate, the (meth)acrylic acid ester copolymers can comprise 1.0 to 65% by weight, based on the total weight of the comonomer phase, of xcex1-olefins, such as ethylene or propylene, and/or vinyl aromatics, such as styrene, and/or vinyl halides, such as vinyl chloride and/or ethylenically unsaturated dicarboxylic acid esters or derivatives thereof, such as diisopropyl-fumarate or the dimethyl, methyl t-butyl, dibutyl and diethyl esters of maleic acid or fumaric acid, or maleic anhydride.
In a preferred embodiment, the vinyl ester copolymers and the (meth)acrylic acid ester copolymers also comprise 0.05 to 10.0% by weight, based on the total weight of the comonomer mixture, of auxiliary monomers from the group consisting of ethylenically unsaturated carboxylic acids, preferably acrylic acid or methacrylic acid; from the group consisting of ethylenically unsaturated carboxylic acid amides, preferably acrylamide; from the group consisting of ethylenically unsaturated sulfonic acids and salts thereof, preferably vinyl-sulfonic acid; and/or from the group consisting of polyethylenically unsaturated comonomers, for example divinyl adipate, diallyl maleate, allyl methacrylate or triallyl cyanurate. Suitable auxiliary monomers are also comonomers having a crosslinking action, for example acrylamidoglycolic acid (AGA), methacrylamidoglycolic acid methyl ester (MAGME), N-methylolacrylamide (NMAA), N-methylolmethacrylamide, allyl N-methylolcarbamate and alkyl ethers, such as the isobutoxy ether, or esters of N-methylolacrylamide, of N-methylolmethacrylamide or allyl N-methylolcarbamate.
Corresponding statements to those for the (meth)acrylic acid ester copolymers apply to the copolymers of esters of maleic or fumaric acid.
The water-insoluble polymers mentioned which can be polymerized by free radicals are preferably prepared by the emulsion polymerization process. The polymerization can be carried out discontinuously or continuously, with or without the use of seed latices, with initial introduction of all the constituents or individual constituents of the reaction mixture, or with initial introduction of a portion and subsequent metering of the constituents or individual constituents of the reaction mixture, or by the metering method without an initial mixture. All the meterings are preferably carried out at the rate of consumption of the particular component. The polymerization is preferably carried out in a temperature range from 0 to 100xc2x0 C., and is initiated using the methods usually employed for emulsion polymerization. The initiation is carried out by means of the customary, water-soluble agents which form free radicals, which are preferably employed in amounts of 0.01 to 3.0% by weight, based on the total weight of the monomers. All the emulsifiers and/or protective colloids usually used in emulsion polymerization can be employed as dispersing agents.
If appropriate, up to 6% by weight, based on the total weight of the monomers, of emulsifier is employed. Possible emulsifiers here are both anionic and cationic as well as nonionic emulsifiers, if these are insoluble in the protective colloid. Protective colloids are preferably employed, particularly preferably in amounts of up to 15% by weight, based on the total weight of the monomers. Examples of these are polyvinyl alcohols and derivatives thereof; such as vinyl alcohol/vinyl acetate copolymers, polyvinylpyrrolidones; polysaccharides in water-soluble form, such as starches (amylose and amylopectin), cellulose, guar, tragacanthic acid, dextran, alginates and carboxymethyl, methyl, hydroxyethyl and hydroxypropyl derivatives thereof; proteins, such as casein, soya protein and gelatin; synthetic polymers, such as poly(meth)acrylic acid, poly(meth)acrylamide, polyvinylsulfonic acids and water-soluble copolymers thereof; melamine-formaldehydesulfonates, naphthalene-formaldehydesulfonates, and styrene/maleic acid and vinyl ether/maleic acid copolymers. In the most preferred embodiment, the polymerization is carried out with a protective colloid and without addition of an emulsifier.
Suitable water-dispersible silicon compounds from the group consisting of silanes, polysilanes, oligosiloxanes, carbosilanes, polycarbosilanes, carbosiloxanes, polycarbosiloxanes and polysilylenedisiloxanes are those which have a boiling point under normal pressure above 160xc2x0 C. Compounds which are preferably employed are silanes, such as tetraorganosilanes SiR4, silicic acid esters Si(ORxe2x80x2)4, organoorganoxysilanes SiRn(ORxe2x80x2)4xe2x88x92n, where n=1 to 3, polysilanes of the general formula R3Si(SiR2)nSiR3 where n=0 to 500, preferably 0 to 8, and oligosiloxanes of the general formula R3SiO(SiR2O)nSiR3 where n=0 to 4, in which Rxe2x80x2 represents identical or different alkyl radicals or alkoxyalkylene radicals having 1 to 4 C atoms, and preferably denotes methyl or ethyl, and R is identical or different and denotes branched or unbranched alkyl radicals having 1 to 22 C atoms, cycloalkyl radicals having 3 to 10 C atoms, alkylene radicals having 2 to 4 C atoms, or aryl, aralkyl or alkylaryl radicals having 6 to 18 C atoms, it also being possible for the radicals R mentioned to be substituted by halogens, such as F or Cl, or by ether, thio-ether, ester, amide, nitrile, hydroxyl, amine, carboxyl, sulfonic acid, carboxylic acid anhydride and carbonyl groups, and in which, in the case of the polysilanes and oligosiloxanes, R can also have the meaning ORxe2x80x2.
Particularly preferred silicon compounds are, for example, tetraethoxysilane, methyltripropoxysilane, methyltri(ethoxyethoxy)silane, vinyltri(methoxyethoxy)silane, (meth)acryloxypropyltriethoxy- or -trimethoxysilane, xcex3-chloropropyltriethoxysilane, xcex2-nitriloethyltriethoxysilane, mercaptopropyltriethoxy- or -trimethoxysilane, phenyltriethoxysilane, iso-octyltriethoxysilane, dipropyldiethoxysilane, methylphenyldiethoxysilane, diphenyldimethoxysilane, methylvinyltri(ethoxyethoxy)silane and di- and/or trisiloxanes thereof. Hexamethyldiethoxytrisiloxane, octamethylcyclotetrasiloxane, tetra-methyldiethoxydisilane, trimethyltrimethoxydisilane, dimethyltetramethoxydisilane, or condensation products thereof, and pentamethyldisilane-disiloxane may furthermore be mentioned. The silicon compounds mentioned can be employed by themselves or as a mixture.
The organosilicon compounds can be prepared by processes such as are described in Noll, Chemie und Technologie der Silicone [Chemistry and technology of the silicones], 2nd edition 1968, Weinheim and in Houben-Weyl, Methoden der organischen Chemie [Methods of organic chemistry], Volume E20, page 1782 et seq., 2219 et seq., Georg Thieme Verlag, Stuttgart, 1987.
The water-dispersible organosilicon compounds are preferably present in an amount of 0.5 to 15% by weight, based on the organopolymer content.
The silicon compounds are preferably added in the form of an emulsion to the organopolymer dispersion to be sprayed. The protective colloids below, if appropriate in combination with suitable emulsifiers, are preferably used for the emulsification. Possible emulsifiers here are both anionic and cationic as well as nonionic emulsifiers. Those which are not soluble in the protective colloid and have relative molecular weights, in contrast to the protective colloids, of less than 2000 are preferred. Suitable emulsifiers are known to. the expert and are to be found, for example, in Houben-Weyl, Methoden der organischen Chemie [Methods of organic chemistry], Volume XIV, 1, Makromolekulare Stoffe [Macromolecular substances], Georg Thieme Verlag, Stuttgart, 1961, 192-208. The emulsifiers are as a rule employed in amounts of up to 5% by weight, based on the silicon compounds. The amount is preferably  less than 1% by weight, based on the organopolymers.
In a preferred embodiment, the dispersion powder composition comprises 8 to 50% by weight, preferably 10 to 25% by weight, of protective colloid, based on the total amount of water-insoluble. organopolymer and silicon compound. Suitable protective colloids are, for example, polyvinyl alcohols and derivatives thereof; polysaccharides in water-soluble form, such as starches (amylose and amylopectin), cellulose, guar, tragacanthic acid, dextran, alginates and carboxymethyl, methyl, hydroxyethyl and hydroxypropyl derivatives thereof; proteins, such as casein, soya protein and gelatin; synthetic polymers, such as poly(meth)acrylic acid, poly(meth)acrylamide, polyvinylsulfonic acids and water-soluble copolymers thereof; melamine-formaldehydesulfonates, naphthalene-formaldehydesulfonates, and styrene/maleic acid and vinyl ether/maleic acid copolymers.
Further constituents of the dispersion powder composition which preferred embodiments comprise are antiblocking agents, such as Ca carbonate or Mg carbonate, talc, gypsum, silicic acid and silicates having particle sizes preferably in the range from 10 nm to 10 xcexcm.
The dispersion powder composition is prepared by means of spray drying. Drying is carried out here in the customary spray drying units, it being possible for the atomization to be effected by means of one-, two- or multi-component nozzles or with a rotating disc. The discharge temperature is in general chosen in the range from 55xc2x0 C. to 100xc2x0 C., preferably 70xc2x0 C. to 90xc2x0 C., depending on the unit, the Tg of the resin and the desired degree of drying.
A mixture of the polymer dispersion, preferably having a solids content of 20 to 60%, and the emulsion or, if appropriate, dispersion of the silicon compound, preferably having a solids content of 20 to 50%, if appropriate after addition of further auxiliaries, can be sprayed and dried together in the spray drying. Particles which comprise the water-insoluble organopolymer particles and the particles of the silicon compound in a matrix of water-soluble protective colloid are obtained here.
As an alternative to this procedure, the aqueous organopolymer dispersion and the aqueous emulsion or, if appropriate, dispersion of the silicon compound can be sprayed through separate nozzles and dried together in the spray tower, if appropriate after addition of further auxiliaries. With this procedure, the organopolymer particles and the particles of the silicon compounds are usually present as separate particles.
The dispersion powder composition can be employed in the typical fields of use. For example, in chemical building products in combination with inorganic, hydraulically setting binders, such as cements (Portland, aluminate, trass, Hullen, magnesia or phosphate cement), gypsum or water-glass, for the preparation of building adhesives, plasters, stopper compositions, flooring stopper compositions, joint mortars and paints. Furthermore as sole binders for coating compositions and adhesives or as binders for textiles. The dispersion powder composition is preferably employed as a hydrophobizing binder in fields of use where, in addition to good adhesion, a reduced uptake of water and/or a water-repellent effect is desired.